Antifungal Wallboards and Building Materials and Methods for the Production Thereof

ABSTRACT

The present invention relates to, inter alia, methods for the treatment of wallboards and the treated wallboards. In particular, the invention relates to the treatment of wallboards with a fungicidally effective amount of a strobilurin or strobilurin-type fungicide. In a particular embodiment the fungicide is azoxystrobin. The invention also provides for the treatment of wallboards and building materials with combinations of fungicides present in synergistic amounts.

The present invention relates to methods for the treatment of wallboardsand the treated wallboards. In particular, the invention relates to thetreatment of wallboards with a fungicidally effective amount of astrobilurin or strobilurin-type fungicide. More specifically, thefungicide is azoxystrobin. More specifically, the treatment comprises afungicidally effective amount of a strobilurin, such as azoxystrobin, orstrobilurin-type fungicide and a further fungicide such as one selectedfrom the group consisting of: thiabendazole, fludioxonil, propiconazoleand difenoconazole.

The fungi of relevance to the invention are those which are capable ofgrowing on building materials such as wallboards. Fungi are versatileorganisms and the substrate on which they grow can include buildingmaterials since such materials can be made of, or have applied to them,substances which support fungal growth. Fungal growth generally requiresdampness, that can be caused on building materials by, for example,internal water leaks or external leaks, or by areas of high humidity orcondensation. Fungal growth also requires a food source which, in thiscase, can be the building material itself or can be dirt or othernutritious material present on the building material.

Fungi which are capable of growing on building materials such aswallboards have been problematic for some time. Obvious effects of suchfungi are discoloration of the material on which they grow, oftenaccompanied by unpleasant smells. Fungi also contribute to the physicaldestruction of the material. In recent years, such fungi have also beenan increasing cause for concern in relation to human health. Varioushealth problems have been attributed to such fungi with most commonbeing allergic reactions and in some cases, human infection. Certainfungi which are capable of growing on such building materials are alsothought to be carcinogenic. Clearly these fungi are perceived as agrowing threat to humans.

We have now found that certain fungicides, that were previously knownfor agricultural use, are surprisingly effective against fungi that arecapable of growing on/infesting building materials such as wallboards.Agricultural use means application to crop plants or harvestedagricultural products such as seeds. This invention represents asignificant step forward in fungal control on building materials, inparticular wallboards.

According to the present invention there is provided a method for theprevention and/or treatment of growth and/or infestation of a fungus ona wallboard comprising treating said wallboard with a fungicidallyeffective amount of a strobilurin or strobilurin-type fungicide.

Strobilurin and strobilurin-type fungicides are a well-known class offungicides that act by inhibiting mitochondrial respiration by blockingelectron transfer between cytochrome b and cytochrome cl at theubiquinol oxidising site. They include the methoxyacrylate strobilurinssuch as azoxystrobin and picoxystrobin, the oximinoacetate strobilurinssuch as kresoxim-methyl and trifloxystrobin, the oximinoacetamidestrobilurins such as dimoxystrobin, metominostrobin, orysastrobin (BAS520) and the strobilurin of the formula:

the dihydrodioxazine strobilurins such as fluoxastrobin, themethoxycarbamate strobilurins such as pyraclostrobin, the strobilurin ofthe formula:

the imidazolinones strobilurin-types such as fenamidone, and theoxazolidinedione strobilurin-types such as famoxadone. Of particularinterest is azoxystrobin. Azoxystrobin is also described as entry 47 inThe Pesticide Manual, Thirteenth Edition, published by The British CropProtection Council, 2003. Picoxystrobin is also described in thePesticide Manual as entry 647.

Wallboard (also sometimes known as drywall or plasterboard) is abuilding material commonly used to make the internal dividing walls ofbuildings. Buildings include residential buildings such as houses andflats and commercial buildings such as shops, warehouses, hotels andfactories and the like, also institutional buildings such as colleges.Wallboard includes ceiling board which is material used for internalceilings. Wallboard is generally in the form of a flat sheet between 0.5and 2 cm thick and comprises, usually, a gypsum core, usually coated onboth sides, with paper. Wallboard is usually fixed to a wooden frame toform an internal wall, or fixed to ceiling spars to form an internalceiling. Wallboard has many desirable properties, such as beingrelatively light and easy to cut, and having a surface that is easilydecorated with paint or wallpaper. However, wallboard suffers from aparticular problem if it is exposed to water and for that reason its useis restricted to internal areas of buildings. Gypsum is verywater-absorbent, and once wet can take a long time to dry out. Thecombination of a damp gypsum core and the starch and cellulose in thepaper on the surface provide an ideal substrate for fungi to grow.Essentially, the damp gypsum provides a convenient sustained waterreservoir for the fungus while the paper provides nutrition. Even whenused internally, wallboards can be exposed to water for example fromleaky internal plumbing or from rainwater leaks from the outside of thebuilding, or from sustained high humidity or condensation. Such leaksare unfortunately rather common and so fungal growth on wallboards is acontinuing problem.

Fungi are at least in part responsible for so-called ‘black mould’, afungal infestation of buildings. Wallboard is particularly susceptibleto black mould, which has become a significant problem in buildings insome areas, and which has been blamed for a range of human healthproblems. Fungi are also responsible for facilitating discoloration ofthe material on which they grow and are a particular problem inresidential buildings.

In a further aspect of the invention there is provided a method for theprevention and/or treatment of growth and/or infestation of a fungus ona wallboard comprising treating said wallboard with a fungicidallyeffective amount of a composition which comprises as active ingredients,synergistic amounts of: (a) a strobilurin or strobilurin-type fungicideand

(b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof.

We have also identified that surprisingly fludioxonil synergises theactivity of strobilurin/strobilurin-type fungicides and thiabendazoleand in particular mixtures of azoxystrobin and thiabendazole againstcertain fungi. More specifically, the addition of small amounts offludioxonil can powerfully increase the antifungal activity ofparticular fungicides against particular fungi that are deleterious towallboards and other materials including building materials, paper,woods and plastics.

Fludioxonil is listed as entry 368 The Pesticide Manual, ThirteenthEdition, published by The British Crop Protection Council, 2003.Fludioxonil is mainly known as a fungicide for use on crops and also asa seed treatment. Thiabendazole is listed as entry 790, difenoconazoleis listed as entry 247 and propiconazole is listed as entry 675.

In a particular embodiment the present invention describes and uses amixture of azoxystrobin and thiabendazole wherein these compounds arepresent in synergistic amounts. In a further embodiment the presentinvention describes and uses a mixture of azoxystrobin, thiabendazoleand fludioxonil wherein these compounds are present in synergisticamounts.

In a further embodiment said strobilurin fungicide is azoxystrobin. In afurther embodiment said strobilurin fungicide is picoxystrobin.

The present invention still further provides a method as described abovewherein the fungus is selected from the group consisting of: Alternariasp.; Penicillium sp.; Aspergillus sp.; Aureobasidium sp.; andStachybotrys sp.

In a particular embodiment the fungus is Stachybotrys atra. Throughoutthis specification Stachybotrys atra is interchangeable withStachybotrys chartarum. In a further embodiment the fungus is Alternariatenuissima. In a still further embodiment the fungus is Penicilliumchrysogeizum. In a still further embodiment the fungus is Aspergillusniger. In a still further embodiment the fungus is Aspergillusversicolor. In a still further embodiment the fungus is Aureobasidiumpullulans. In a still further embodiment the fungus is a combination ofthose mentioned above, in particular Alternaria tenuissima, Penicilliumchrysogenum, Aspergillus niger and Aspergillus versicolor. In a stillfurther embodiment the fungus is Aureobasidium pullulans andStachybotrys chartarum.

Examples of other problematic fungi are: Alternaria alternata,Aspergillus flavus, Aspergillus terreus, Aspergillus fumigatus,Aspergillus repens, Aspergillus veisicolor, Candida albicans, Chaetomiumglobosum, Cladosporium cladosporioides, Cladosporium herbaruin,Cladosporium sphaerospermum, Coniophora puteana, Curvularia genticulata,Diplodia natalensis, Epidermophyton floccosum, Fusarium oxysporum,Gliocladium virens, Gloeophyllum trabeum, Humicola grisea, Lecythophoramutabilis, Lentinus cyathiformis, Lentinus lepidus, Memnionellaechinata, Mucor indicus, Mucor racemosus, Oligoporus placenta,Paecilomyces variotii, Penicillium citrinum, Penicillium funiculosum,Penicillium ochrochloron, Penicillium purpurogenum, Penicilliumpinophilum, Penicillium variabile, Petriella setifera, Phanerochaetechrysosporium, Phoma violacea, Poria placenta, Rhodotorula rubra,Schizophyllum commune, Sclerophoma phytiophila Scopulariopsisbrevicaulis, Serpula laciymans, Sporobolomyces roseus, Stemphyliumdendriticum, Trichophyton mentagrophytes, Trichurus spiralis,Trichophyton rubrum, Ulocladium atrum and Ulocladium chartarum.

Of particular concern are: Alternaria alternata, Alternaria tenuissima,Aspergillus niger, Aspergillus versicolor, Aureobasidium pullulans,Chaetomium globosum, Cladosporium cladosporioides, Coniophora puteana,Gloeophyllum trabeum, Memnionella echinata, Mucor indicus, Oligoporusplacenta, Penicillium citrinum, Penicillium chrysogenum, Penicilliumfuniculosum, Penicillium pinophilum, Sclerophoma phytiophila,Stachybotrys atra, Stachybotrys chartarum, and Ulocladium chartarum.

The present invention still further provides a method as described abovewherein said wallboard is treated during the manufacturing process ofsaid wallboard.

The present invention still further provides a method as described abovewherein said fungicide or fungicides is/are included in the gypsum coreof said wallboard.

The present invention still further provides a method as described abovein which the fungicide or fungicides is/are applied to the surface ofthe gypsum core of the wallboard.

The present invention still further provides a method as described abovewherein the fungicide or fungicides is/are included in the paper coatingof the wallboard.

The present invention still further provides a method as described abovewherein the fungicide or fungicides is/are included in the paper duringthe papermaking process.

The present invention still further provides a method as described abovewherein the fungicide or fungicides is/are applied to the paper aftersaid paper has been made.

The present invention still further provides a method as described abovewherein the substantially finished wallboard is treated with thefungicide or fungicides.

The present invention still further provides a method as described abovewherein the wallboard is treated with the fungicide or fungicides priorto installation of said wallboard.

The present invention still further provides a method as described abovewherein the wallboard is treated with the fungicide or fungicides afterinstallation of said wallboard.

Treating the finished wallboard can be carried out as part of itsmanufacture or in a separate process, for example in a separatetreatment plant, or on or near the building site where the wallboard isto be installed.

The treatment can be carried out by a number of methods including thosementioned within this specification relating to the treatment ofbuilding materials. In particular, brushing, wiping, rolling orpreferably spraying the surface with a composition containing thefungicide/fungicides of the invention. If infestation with fungi isalready apparent or suspected then the application of thefungicide/fungicides can be preceded by a washing step using eitherconventional cleaning materials such as bleach and/or detergents toremove some or all of the visible mould or staining. Wallboard that wasoriginally treated from new in accordance with the invention can also beretreated by any of these methods, for example to increase or prolongthe fungicidal effect. This retreatment and the process therefor, alsoform part of the present invention.

In a still further aspect of the present invention there is provided amethod for the prevention and/or treatment of fungal contamination on awallboard comprising treating said wallboard with a fungicidallyeffective amount of a strobilurin or strobilurin-type fungicide.

In a still further aspect of the invention there is provided a methodfor the prevention and/or treatment of fungal contamination on awallboard comprising treating said wallboard with a fungicidallyeffective amount of a composition which comprises as active ingredients,synergistic amounts of: (a) a strobilurin or strobilurin-type fungicideand

(b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof.

The present invention still further provides a method as described abovewherein said strobilurin fungicide is azoxystrobin. In a particularembodiment said wallboard is treated with a composition of azoxystrobinand thiabendazole wherein these compounds are present in synergisticamounts. In a further embodiment said wallboard is treated with acomposition of azoxystrobin, thiabendazole and fludioxonil wherein thesecompounds are present in synergistic amounts.

The treatment can be preventative, that is it can be carried out beforethere is visible fungal growth, or it can be curative, that is it can becarried out on wallboard on which fungus is already growing.

The present invention still further provides a wallboard obtainable by amethod as described above.

The present invention still further provides a wallboard obtained by amethod as described above.

In a further aspect of the invention there is provided a wallboard thathas been treated with a fungicidally effective amount of a strobilurinor strobilurin-type fungicide.

In a still further aspect of the invention there is provided a wallboardthat has been treated with a fungicidally effective amount of acomposition which comprises as active ingredients: synergistic amountsof: (a) a strobilurin or strobilurin-type fungicide and

(b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof.

The present invention still further provides a wallboard as describedabove wherein said strobilurin fungicide is azoxystrobin. In a furtherembodiment of the invention said strobilurin fungicide is picoxystrobin.

The present invention still further provides a wallboard as describedabove wherein the fungicides are azoxystrobin and thiabendazole. In afurther embodiment the fungicides are azoxystrobin, thiabendazole andfludioxonil.

The present invention still further provides a wallboard as describedabove wherein the fungicide or fungicides is/are included in the gypsumcore. There are a number of ways to achieve this. For example thefungicide/fungicides can be included in the gypsum core by mixing itwith the gypsum before said gypsum hardens.

The present invention still further provides a wallboard as describedabove wherein the fungicide or fungicides is/are applied to the surfaceof the gypsum core of the wallboard.

The present invention still further provides a wallboard as describedabove wherein the fungicide or fungicides is/are included in the papercoating of the wallboard.

The present invention still further provides a wallboard as describedabove wherein the fungicide or fungicides is/are applied after thewallboard is made.

In a still further aspect of the invention there is provided a wallboardtreated with a fungicidally effective amount of a strobilurin orstrobilurin-type fungicide such that growth of fungi on said wallboardis prevented.

In a still further aspect of the invention there is provided a wallboardtreated with a fungicidally effective amount of a composition whichcomprises as active ingredients, synergistic amounts of: (a) astrobilurin or strobilurin-type fungicide and (b) a fungicide selectedfrom the group consisting of: (bi) thiabendazole; (bii) difenoconazole;(biii) propiconazole; (biv) fludioxonil or a combination thereof, suchthat growth of fungi on said wallboard is prevented. In a particularembodiment said composition comprises as active ingredients (a)azoxystrobin and (bi) thiabendazole in such synergistic amounts. In afurther embodiment said composition comprises as active ingredients (a)azoxystrobin, (bi) thiabendazole and (biv) fludioxonil in suchsynergistic amounts.

In a still further aspect of the invention there is provided a methodfor re-treating a previously treated wallboard comprising applying tosaid wallboard a fungicidally effective amount of a strobilurin orstrobilurin-type fungicide such that fungal contamination of saidwallboard is prevented and/or retarded.

In a still further aspect of the invention there is provided a methodfor treating a wallboard that has been previously treated with adifferent fungicide comprising applying to said wallboard a fungicidallyeffective amount of a strobilurin or strobilurin-type fungicide suchthat fungal contamination of said material is prevented and/or retarded.

Preferably the wallboard comprises a fungicide/fungicides according tothe invention present in concentrations of about 50 ppm to 1000 ppm.

The composition containing the fungicide/fungicides according to theinvention can be based on organic solvents or can be water based.Organic solvents can have the advantage of relatively quick drying, butwater-based compositions are preferred because of their lower airpollution potential, and lower odour, particularly in buildings. Oneexample of a suitable water-based composition is an emulsionconcentrate.

The composition can be chosen from a number of formulation types,including dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, fogging/smoke formulations, capsulesuspensions (CS) and other applicable formulations well known to theperson skilled in the art.

Dustable powders (DP) may be prepared by mixing a fungicide/fungicidesaccording to the invention with one or more solid diluents (for examplenatural clays, kaolin, pyrophyllite, bentonite, alumina,montmorillonite, kieselguhr, chalk, diatomaceous earths, calciumphosphates, calcium and magnesium carbonates, sulphur, lime, flours,talc and other organic and inorganic solid carriers) and mechanicallygrinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a fungicide/fungicideswith one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water-soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a fungicide/fungicideswith one or more solid diluents or carriers, one or more wetting agentsand, preferably, one or more dispersing agents and, optionally, one ormore suspending agents to facilitate the dispersion in liquids. Themixture is then ground to a fine powder. Similar compositions may alsobe granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of afungicide/fungicides according to the invention and one or more powderedsolid diluents or carriers, or from pre-formed blank granules byabsorbing a fungicide/fungicides according to the invention (or asolution thereof, in a suitable agent) in a porous granular material(such as pumice, attapulgite clays, fuller's earth, kieselguhr,diatomaceous earths or ground corn cobs) or by adsorbing afungicide/fungicides according to the invention (or a solution thereof,in a suitable agent) on to a hard core material (such as sands,silicates, mineral carbonates, sulphates or phosphates) and drying ifnecessary. Agents which are commonly used to aid absorption oradsorption include solvents (such as aliphatic and aromatic petroleumsolvents, alcohols, ethers, ketones and esters) and sticking agents(such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars andvegetable oils). One or more other additives may also be included ingranules (for example an emulsifying agent, wetting agent or dispersingagent).

Dispersible Concentrates (DC) may be prepared by dissolving afungicide/fungicides according to the invention in water or an organicsolvent, such as a ketone, alcohol or glycol ether. These solutions maycontain a surface-active agent (for example to improve water dilution orprevent crystallisation in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a fungicide/fungicides according to the inventionin an organic solvent (optionally containing one or more wetting agents,one or more emulsifying agents or a mixture of said agents). Suitableorganic solvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone), alcohols (suchas benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones(such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides offatty acids (such as C₈-C₁₀ fatty acid dimethylamide) and chlorinatedhydrocarbons. An EC product may spontaneously emulsify on addition towater, to produce an emulsion with sufficient stability to allow sprayapplication through appropriate equipment. Preparation of an EW involvesobtaining a fungicide/fungicides according to the invention either as aliquid (if it is not a liquid at room temperature, it may be melted at areasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents that have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. Afungicide/fungicides according to the invention is present initially ineither the water or the solvent/SFA blend. Suitable solvents for use inMEs include those hereinbefore described for use in ECs or in EWs. An MEmay be either an oil-in-water or a water-in-oil system (which system ispresent may be determined by conductivity measurements) and may besuitable for mixing water-soluble and oil-soluble pesticides in the sameformulation. An ME is suitable for dilution into water, either remainingas a microemulsion or forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of afungicide/fungicides according to the invention. SCs may be prepared byball or bead milling a fungicide/fungicides according to the inventionin a suitable medium, optionally with one or more dispersing agents, toproduce a fine particle suspension of the compound. One or more wettingagents may be included in the composition and a suspending agent may beincluded to reduce the rate at which the particles settle. In aparticular embodiment of the invention there is provided a mixture of(azoxystrobin) Amistar® and (thiabendazole) Tecto® or Mertect®.Alternatively, a fungicide/fungicides according to the invention may bedry milled and added to water, containing agents hereinbefore described,to produce the desired end product.

Aerosol formulations comprise a fungicide/fungicides according to theinvention and a suitable propellant (for example n-butane). Afungicide/fungicides according to the invention may also be dissolved ordispersed in a suitable medium (for example water or a water miscibleliquid, such as n-propanol) to provide compositions for use innon-pressurised, hand-actuated spray pumps.

A fungicide/fungicides according to the invention may be mixed in thedry state with a pyrotechnic mixture to form a composition suitable forgenerating, in an enclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa fungicide/fungicides according to the invention and, optionally, acarrier or diluent therefor. The polymeric shell may be produced byeither an interfacial polycondensation reaction or by a coacervationprocedure. The compositions may provide for controlled release of afungicide/fungicides according to the invention. A fungicide/fungicidesaccording to the invention may also be formulated in a biodegradablepolymeric matrix to provide a slow, controlled release of the compound.

The composition may include one or more additives to improve theproperties of the composition (for example by improving wetting,retention or distribution on surfaces; or absorption into surfaces).Such additives include surface-active agents, spray additives based onoils, for example certain mineral oils or natural plant oils (such assoy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a fungicide/fungicides according to the invention).

The compositions of this invention may contain other compounds havingbiological activity, for example compounds having similar orcomplementary fungicidal activity or which possess, insecticidal and/oracaricidal and/or algicidal activity. The fungicide can be combined withother fungicides. Combinations with other fungicides can be used tocontrol a broader range of fungi, which is particularly useful ifmultiple species of fungi are present, or if the species is not known.

The addition of another active ingredient may provide a compositionhaving a broader spectrum of activity or increased persistence at alocus, synergise the activity or complement the activity (for example byincreasing the speed of effect or overcoming repellency) of afungicide/fungicides according to the invention, or help to overcome orprevent the development of resistance to individual components.

Examples of fungicidal compounds which may be included in thecomposition of the invention are AC 382042(N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy) propionamide),acibenzolar-5-methyl, alanycarb, aldimorph, anilazine, azaconazole,azafenidin, benalaxyl, benomyl, benthiavalicarb, biloxazol, bitertanol,blasticidin S, boscalid (new name for nicobifen), bromuconazole,Bronopol, bupirimate, captafol, captan, carbendazim, carbendazimchlorhydrate, carboxin, carpropamid, carvone, CGA 41396, CGA 41397,chinomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate,clozylacon, copper containing compounds such as copper oxychloride,copper oxyquino-late, copper sulphate, copper tallate, and Bordeauxmixture, cyamidazosulfamid, cyazofamid (IKF-916), cyflufenamid,cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide1,1′-dioxide, dichlofluanid, diclocymet, diclomezine, dicloran,diethofencarb, difenzoquat, diflumetorim, diiodomethyl-p-tolylsulfone(Amical, from Dow) O,O-di-iso-propyl-5-benzyl thiophosphate,dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin,diniconazole, dinocap, dithianon, Dithiocarbamates, dodecyl dimethylammonium chloride, dodemorph, dodine, doguadine, edifenphos,epoxiconazole, ethaboxam, ethirimol, ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate,etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram,fenhexamid, fenoxanil (AC 382042), fenpropidin, fenpropimorph, fentinacetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,flumorph, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole,hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine,iminoctadine triacetate, 3-iodo-2-propynyl butylcarbamate (IBPC),ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butylcarbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY 248908, mancozeb, maneb, MBT mefenoxam, mepanipyrim,mepronil, metalaxyl, metalaxyl M, metconazole, metiram, metiram-zinc,metominostrobin, metrafenone, MON65500(N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide),myc-lobutanil, NTN0301, neoasozin, nickel dimethyldithiocarbamate,nitrothale-isopropyl, nuarimol, 2-O-octyl-4-isothiazolin-3-one (Skane M8 Rohm& Hass), ofurace, organomercury compounds, orysastrobin, oxadixyl,oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate,penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide,picoxystrobin, polyoxin D, polyram, probenazole, prochloraz,procymidone, propamocarb, propamocarb hydrochloride, propineb, propionicacid, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, Sodiumand Zinc Pyrithione (Omadine chemistry from Arch Chem.), pyrifenox,pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammoniumcompounds, quinomethionate, quinoxyfen, quintozene, silthiofam (MON65500), S-imazalil, simeconazole, sipconazole, sodiumpentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole,tecloftalam, tecnazene, tetraconazole, thifluzamide,2-(thiocyano-methylthio)benzothiazole, thiophanate-methyl, thiram,tiadinil, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon,triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A,vapam, vinclozolin, XRD-563, zineb, ziram, zoxamide and compounds of theformulae:

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises as activeingredients (a) a strobilurin or strobilurin-type fungicide and (b)thiabendazole and (c) propiconazole wherein said ingredients are presentin synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises as activeingredients (a) a strobilurin or strobilurin-type fungicide and (b)fludioxonil and (c) propiconazole wherein said ingredients are presentin synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) difenoconazole and (c)thiabendazole wherein the fungicides are present in synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) difenoconazole and (c)fludioxonil wherein the fungicides are present in synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) thiabendazole and (c)fludioxonil wherein the fungicides are present in synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) difenoconazole and (c)propiconazole wherein the fungicides are present in synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) propiconazole whereinthe fungicides are present in synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) fludioxonil whereinthe fungicides are present in synergistic amounts.

In a still further aspect of the invention there is provided a mixturefor use in the present invention which mixture comprises (a) astrobilurin or strobilurin-type fungicide and (b) difenoconazole whereinthe fungicides are present in synergistic amounts.

In a particular embodiment said strobilurin fungicide is azoxystrobin.

Some mixtures may comprise active ingredients that have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

A dye can also be included in the compositions. This can be useful todifferentiate treated wallboard from untreated wallboard. When thewallboard is new this provides a simple visual identifier for warehouseoperators and construction workers. A dye can also be useful when thecomposition is applied to wallboard that has already been installed toidentify those areas to which fungicide has been applied, for examplewhen spraying a large area. It is useful for the applicators to seewhere they have applied the composition particularly when multipleoperators are carrying out the application, or when the applicationprocess carried out over a number of days. It also allows easyinspection so that supervisors and surveyors can see what has beentreated. It is also possible to use the depth of the colour as a guideto the amount of fungicide applied, particularly when it is applied tothe wallboard surface. The depth of colour can be assessed visually, ora calorimeter can be used.

The present invention still further provides a building comprising awallboard as described above. In a particular embodiment said buildingis a temporary building. In a further embodiment said building is apermanent structure. In a still further embodiment said buildingcomprises a plurality of wallboards as described above.

In a still further aspect of the invention there is provided the use ofa fungicidally effective amount of a strobilurin or strobilurin-typefungicide in a method of controlling fungal growth on a wallboard.

In a still further aspect of the invention there is provided the use ofa fungicidally effective amount of a composition which comprises asactive ingredients synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and (b) a fungicide selected from the groupconsisting of: (bi) thiabendazole; (bii) difenoconazole; (biii)propiconazole; (biv) fludioxonil or a combination thereof in a method ofcontrolling fungal growth on a wallboard.

In a still further aspect of the invention there is provided the use ofa fungicidally effective amount of a strobilurin or strobilurin-typefungicide in the production of a fungicidally treated wallboard.

In a still further aspect of the invention there is provided the use ofa fungicidally effective amount of a composition which comprises asactive ingredients, synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and (b) a fungicide selected from the groupconsisting of: (bi) thiabendazole; (bii) difenoconazole; (biii)propiconazole; (biv) fludioxonil or a combination thereof in theproduction of a fungicidally treated wallboard.

The present invention still further provides the use as described abovewherein said strobilurin fungicide is azoxystrobin. In a still furtherembodiment, the present invention provides for the use as describedabove wherein said strobilurin fungicide is picoxystrobin.

In a still further aspect of the invention there is provided a kitcomprising a fungicidally effective amount of a strobilurin orstrobilurin-type fungicide and a wallboard and a means for applying saidfungicide to said wallboard.

In a still further aspect of the invention there is provided a kitcomprising a fungicidally effective amount of a synergistic compositionwhich comprises as active ingredients: (a) a strobilurin orstrobilurin-type fungicide and (b) a fungicide selected from the groupconsisting of: (bi) thiabendazole; (bii) difenoconazole; (biii)propiconazole; (biv) fludioxonil or a combination thereof and awallboard and a means for applying the fungicides to said wallboard.

In a still further aspect of the invention there is provided a kitcomprising a fungicidally effective amount of azoxystrobin and awallboard and a means for treating said wallboard with saidazoxystrobin.

In a still further aspect of the invention there is provided a kitcomprising a fungicidally effective amount of azoxystrobin andthiabendazole and a wallboard and a means for treating said wallboardwith said azoxystrobin and said thiabendazole.

In a still further aspect of the invention there is provided acomposition suitable for use in the treatment of a wallboard comprisingas active ingredients synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and (b) a fungicide selected from the groupconsisting of: (bi) thiabendazole; (bii) difenoconazole; (biii)propiconazole; (biv) fludioxonil or a combination thereof. In aparticular embodiment said composition comprises azoxystrobin andthiabendazole. In a further embodiment said composition comprisesazoxystrobin, thiabendazole and fludioxonil.

In a still further aspect of the invention there is provided acomposition suitable for use in the treatment of a wallboard consistingof, synergistic amounts of: (a) a strobilurin or strobilurin-typefungicide and (b) a fungicide selected from the group consisting of:(bi) thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof and a fungicidally acceptablecarrier and/or adjuvant. In a particular embodiment said compositionconsists of azoxystrobin and thiabendazole and a fungicidally acceptablecarrier and/or adjuvant. In a further embodiment said compositionconsists of azoxystrobin, thiabendazole and fludioxonil and afungicidally acceptable carrier and/or adjuvant.

In a still further aspect of the invention there is provided a methodfor protecting wood from infestation with Coniophora puteana comprisingtreating said wood with a strobilurin or strobilurin-type fungicide.

In a still further aspect of the invention there is provide a method forthe prevention of fungal infection induced wet-rot in wood comprisingtreating said wood with a strobilurin or strobilurin-type fungicide.

In a still further aspect of the invention there is provided a methodfor the prevention and/or treatment of Coniophora puteanagrowth/infestation on wood comprising treating said wood with afungicidally effective amount of a strobilurin or strobilurin-typefungicide

The present invention further provides a method as described abovewherein said strobilurin fungicide is azoxystrobin.

The present invention still further provides a method as described abovewherein said treatment additionally comprises treatment with a fungicideselected from the group consisting of: (bi) thiabendazole; (bii)difenoconazole; (biii) propiconazole; (biv) fludioxonil or a combinationthereof.

In a still further aspect of the invention there is provided acomposition comprising as active ingredients, synergistic amounts of:(a) a strobilurin or strobilurin-type fungicide and (b) a fungicideselected from the group consisting of: (bi) thiabendazole; (bii)difenoconazole; (biii) propiconazole; (biv) fludioxonil or a combinationthereof. In a particular embodiment said composition comprisesazoxystrobin and thiabendazole. In a further embodiment said compositioncomprises azoxystrobin, thiabendazole and fludioxonil.

In a still further aspect of the invention there is provided acomposition consisting of synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and

(b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof and a fungicidally acceptablecarrier and/or adjuvant. In a particular embodiment said compositionconsists of azoxystrobin and thiabendazole and a fungicidally acceptablecarrier and/or adjuvant. In a further embodiment said compositionconsists of azoxystrobin, thiabendazole and fludioxonil and afungicidally acceptable carrier and/or adjuvant.

In a still further aspect of the invention there is provided acomposition suitable for use in the treatment of a wallboard comprisingas active ingredients, synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and (b) thiabendazole.

In a still further aspect of the invention there is provided acomposition suitable for use in the treatment of a wallboard consistingof synergistic amounts of: (a) a strobilurin or strobilurin-typefungicide and (b) thiabendazole and a fungicidally acceptable carrierand/or adjuvant. In a particular embodiment said composition consists ofazoxystrobin, thiabendazole and fludioxonil and a fungicidallyacceptable carrier and/or adjuvant.

In a still further aspect of the invention there is provided acomposition suitable for use in the treatment of wood comprising afungicidally effective amount of a composition which comprises as activeingredients, synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and (b) a fungicide selected from the groupconsisting of: (bi) thiabendazole; (bii) difenoconazole; (biii)propiconazole; (biv) fludioxonil or a combination thereof.

In a still further aspect of the invention there is provided acomposition suitable for use in the treatment of wood consisting ofsynergistic amounts of: (a) a strobilurin or strobilurin-type fungicideand (b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof and a carrier and/or adjuvant.

The present invention still further provides a composition as describedabove wherein said strobilurin fungicide is azoxystrobin.

Suitable carriers and adjuvants may be solid or liquid and are, forexample, natural or regenerated mineral substances, solvents,dispersants, wetting agents, tackifiers, thickeners, binders orfertilisers. They are conveniently formulated in known manner to form,for example, emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions, dilute emulsions, wettable powders,soluble powders, dusts, granules or capsules, for instance byencapsulation in polymers substances. As with the nature of thecomposition, the method of application, such as spraying, atomising,dusting, scattering, coating or pouring, is chosen in accordance withthe prevailing circumstances.

The formulations may be prepared in known manner, typically byintimately mixing, grinding and/or extruding the fungicide/fungicidesaccording to the invention with an extender, for example, a solvent or asolid or liquid carrier and, where appropriate, one or moresurface-active compounds (surfactants).

In a still further aspect of the invention there is provided a methodfor the prevention and/or treatment of fungal growth/infestation onpaper comprising treating said paper with a composition which comprisesas active ingredients synergistic amounts of: (a) a strobilurin orstrobilurin-type fungicide and (b) a fungicide selected from the groupconsisting of: (bi) thiabendazole; (bii) difenoconazole; (biii)propiconazole; (biv) fludioxonil or a combination thereof. In aparticular embodiment said composition comprises azoxystrobin andthiabendazole. In a further embodiment said composition comprisesazoxystrobin, thiabendazole and fludioxonil.

In a still further aspect of the invention there is provided a paperproduct comprising a composition which comprises as active ingredientssynergistic amounts of: (a) a strobilurin or strobilurin-type fungicideand (b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof. In a particular embodiment saidcomposition comprises azoxystrobin and thiabendazole. In a furtherembodiment said composition comprises azoxystrobin, thiabendazole andfludioxonil.

In a still further aspect of the invention there is provided a paperproduct comprising, as active ingredients, synergistic amounts of: (a) astrobilurin or strobilurin-type fungicide and (b) a fungicide selectedfrom the group consisting of: (bi) thiabendazole; (bii) difenoconazole;(biii) propiconazole; (biv) fludioxonil or a combination thereof. In aparticular embodiment said paper product comprises azoxystrobin andthiabendazole. In a further embodiment said paper product comprisesazoxystrobin, thiabendazole and fludioxonil.

In a still further aspect of the invention there is provided a methodfor the prevention and/or treatment of fungal growth/infestation in aheat exchange system comprising treating said system with a compositionwhich comprises as active ingredients synergistic amounts of: (a) astrobilurin or strobilurin-type fungicide and (b) a fungicide selectedfrom the group consisting of: (bi) thiabendazole; (bii) difenoconazole;(biii) propiconazole; (biv) fludioxonil or a combination thereof. In aparticular embodiment said composition comprises azoxystrobin andthiabendazole. In a further embodiment said composition comprisesazoxystrobin, thiabendazole and fludioxonil.

In a still further aspect of the invention there is provided a coolinglubricant comprising a composition which comprises as active ingredientssynergistic amounts of: (a) a strobilurin or strobilurin-type fungicideand (b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof. In a particular embodiment saidcomposition comprises azoxystrobin and thiabendazole. In a furtherembodiment said composition comprises azoxystrobin, thiabendazole andfludioxonil.

The synergistic fungicidal mixtures of the present invention may also beused in the protection and/or treatment of cooling and heating systems,ventilation and air conditioning systems and parts of production plants,for example cooling-water circuits.

The synergistic composition may be applied to the material referred toabove in a manner as described above and the fungicides may be appliedin a ratio as defined in the examples.

In a still further aspect of the invention there is provided a methodfor the prevention and/or treatment of fungal growth/infestation on abuilding material comprising treating said material with a fungicidallyeffective amount of a strobilurin or strobilurin-type fungicide.

In a still further aspect of the invention there is provided a methodfor the prevention and/or treatment of fungal growth/infestation on abuilding material comprising treating said material with a fungicidallyeffective amount of a composition which comprises as active ingredientssynergistic amounts of: (a) a strobilurin or strobilurin-type fungicideand (b) a fungicide selected from the group consisting of: (bi)thiabendazole; (bii) difenoconazole; (biii) propiconazole; (biv)fludioxonil or a combination thereof. In a particular embodiment saidcomposition comprises azoxystrobin and thiabendazole. In a furtherembodiment said composition comprises azoxystrobin, thiabendazole andfludioxonil. The synergistic composition may be applied to the buildingmaterial in a manner as described above and the fungicides may beapplied in a ratio as defined in the examples.

In a particular embodiment of the invention said strobilurin orstrobilurin-type fungicide is azoxystrobin.

“building material” means those materials used for construction and thelike. In particular, building material includes structural timber,doors, cupboards, storage units, carpets, particularly natural fibrecarpets such as wool and hessian, paints, plastics, wood (includingengineered wood) and wood plastic composite. In addition to this,building material includes adhesives, sealants, joining materials andjoints and insulation material. In a particular embodiment “buildingmaterial” means structural timber. In a further embodiment “buildingmaterial” means engineered wood. In a further embodiment “buildingmaterial” means plastic. Plastics includes plastic polymers andcopolymers, including: acrylonitrile butadiene styrene, butyl rubber,epoxies, fluoropolymers, isoprene, nylons, polyethylene, polyurethane,polypropylene, polyvinyl chloride, polystyrene, polycarbonate,polyvinylidene fluoride, polyacrylate, polymethyl methacrylate,polyurethane, polybutylene, polybutylene terephthalate, polyethersulfone, polyphenyllenoxide, polyphenylene ether, polyphenylene sulfide,polyphtatamide, polysulphene, polyester, silicone, styrene butadienerubber and combinations of polymers. In a further embodiment “buildingmaterial” means polyvinyl chloride (PVC). In a further embodiment“building material” means polyurethane (PU). In a further embodiment“building materials” means paint. In a further embodiment “buildingmaterial” means wood plastic composite (WPC). Wood plastic composite isa material that is well known in the art. A review of WPCs can be foundin the following publication—Craig Clemons—Forrest Products Journal.June 2002 Vol 52. No. 6. pp 10-18.

“Wood” is to be understood as meaning wood and wood products, forexample: derived timber products, lumber, plywood, chipboard,flakeboard, laminated beams, oriented strandboard, hardboard, andparticleboard, tropical wood, structural timber, wooden beams, railwaysleepers, components of bridges, jetties, vehicles made of wood, boxes,pallets, containers, telegraph-poles, wooden fences, wooden lagging,windows and doors made of wood, plywood, chipboard, joinery, or woodenproducts which are used, quite generally, for building houses or decks,in building joinery or wood products that are generally used inhouse-building including engineered wood, construction and carpentry.

The methods of the invention can be used in the prevention and/ortreatment of the growth/infestation by/of a fungus as described withinthis specification. The fungus can be controlled by treating the fungusor the building material with a fungicide/synergistic compositionaccording to the invention in a convenient manner. Examples of ways inwhich the fungus or building material can be treated with a fungicideaccording to the invention are: by including said fungicide in thebuilding material itself, absorbing, impregnating, treating (in closedpressure or vacuum systems) said material with said fungicide, dippingor soaking the building material, or coating the building material forexample by curtain coating, roller, brush, spray, atomisation, dusting,scattering or pouring application.

In a still further aspect of the invention there is provided a methodfor producing a treated building material comprising applying afungicidally effective amount of the fungicide/fungicides according tothe invention to said material such that fungal contamination of saidmaterial is prevented and/or retarded.

In a still further aspect of the invention there is provided a methodfor re-treating a treated building material comprising applying to saidmaterial a fungicidally effective amount of the fungicide/fungicidesaccording to the invention such that fungal contamination of saidmaterial is prevented and/or retarded.

The present invention still further provides a building materialobtainable by a method as described above.

In a still further aspect of the invention there is provided a buildingmaterial treated with a fungicidally effective amount of afungicide/fungicides according to the invention such that growth offungi on said material is prevented.

The present invention still further provides a building comprising abuilding material as described above. In a particular embodiment saidbuilding is a temporary building. In a further embodiment said buildingis a permanent structure.

In a still further aspect of the invention there is provided the use ofa fungicide/fungicides according to the invention in a method oftreating a building material to prevent and/or treat growth and/orinfestation of a fungus as described above on said material.

In a still further aspect of the invention there is provided a kit ofparts comprising fungicide/fungicides according to the invention and ameans for applying said fungicide/fungicides to a building material.

In a still further aspect of the invention there is provided a kit ofparts comprising fungicide/fungicides according to the invention and abuilding material and a means for applying said fungicide/fungicides tosaid building material.

The present invention still further provides a method as described abovewherein the fungi comprises Coniophora puteana. In a particularembodiment said method prevents and/or treats growth/infestation ofConiophora puteana. In a still further embodiment there is provided amethod as described above wherein said fungicidally effective amountcomprises an amount of fungicide that is capable of preventing and/ortreating growth or infestation of Coniophora puteana.

In a particular embodiment the fungicide/fungicides may be applied by ameans as described above. In particular, said fungicide may be appliedby a means selected from: a roller, brush, spray, atomisation, means fordusting, scattering or pouring.

The invention will now be described with reference to the followingexamples:

EXAMPLES Example 1

Wallboard paper samples treated with Azoxystrobin/thiabendazole usingASTM test method no. ASTM D 3273-00.

ASTM D 3273-00, Standard Test Method for Resistance to Growth of Mold onthe Surface of Interior Coatings in an Environmental Chamber. ASTMInternational, 100 Barr Harbor Drive, PO Box C700, West Conshohocken,Pa. 19428-2959, United States. The method involves suspending papersheets in an environmental chamber held at 32+/−1 degree Celsius at95-98% relative humidity. The floor of the chamber holds a tray of soilthat is inoculated with Aureobasidium pullulans (ATCC 9348), Aspergillusniger (ATCC 6275) & Penicillium sp (ATCC 9849) according to the method.The organisms sporulate in the soil and provide a continuous inoculum.Growth is rated after an appropriate time period (in this case 90 days)by visual assessment of surfaces compared to a set of photographicstandards.

Table 1 below provides the average scores obtained. The applicationcolumn relates to the rate of the active ingredients in pounds of activeingredient applied to the paper per ton of paper. The paper test samplesare rated for defacement caused by fungal growth. The rating scale isfrom 0 to 10, where 0=complete defacement and 10=no defacement. Ratingswere taken at 60, 90 and 120 days after inoculation.

TABLE 1 Results Application Rate lb 60 Days 90 Days 120 Days active/tonCreamface Greyback Creamface Greyback Creamface Greyback Treatment paperPaper Paper Paper Paper Paper Paper Thiabendazole - Mertect ™ TBZ 0.16.00 7.67 4.00 8.00 5.00 9.00 340F Thiabendazole - Mertect ™ TBZ 0.57.67 7.33 5.33 7.00 7.33 6.67 340F Thiabendazole - Mertect ™ TBZ 1.09.00 8.00 8.67 7.67 10.00 9.67 340F Thiabendazole - Mertect ™ TBZ 3.09.33 9.67 9.00 10.00 9.00 10.00 340F Thiabendazole - Mertect ™ TBZ 5.09.33 9.33 8.33 9.00 9.00 10.00 340F Azoxystrobin - Heritage ™ AZO 0.19.00 10.00 7.33 10.00 7.00 10.00 50DF Azoxystrobin - Heritage ™ AZO 0.58.67 10.00 8.33 9.67 8.67 10.00 50DF Azoxystrobin - Heritage ™ AZO 1.09.33 10.00 9.00 8.67 9.00 10.00 50DF Azoxystrobin - Heritage ™ AZO 3.09.67 10.00 8.33 8.33 8.67 10.00 50DF Azoxystrobin - Heritage ™ AZO 5.09.33 10.00 8.33 9.00 8.00 10.00 50DF Thiabendazole/Azoxystrobin TBZ/AZO10.00 10.00 10.00 10.00 10.00 10.00 Mixture 1.0/1.0

Example 2 Comparison of a Strobilurin Fungicide (Azoxystrobin) AgainstOther Fungicides;

1. Propagation

Stem cultures of Coniophora puteana were produced by propagating thefungus on a growth medium comprising yeast extract (10 g), glycerol (20ml), magnesium sulphate (0.5 g), sodium nitrate (6.0 g), potassiumchloride (0.5 g), potassium dihydrogen orthophosphate (1.5 g), agar (20g) in distilled water (980 ml).

2. Test

Fungicides were added at levels of 5000, 100, 10, 1, 0.1 and 0.01 mgfungicide/litre of growth medium (described above) to give fivedifferent growth medium compositions for each fungicide. Mycelial plugswere taken from the stem cultures and transferred upside down onto petridishes containing the fungicide amended agar.

3. Assessment

The radial mycelial growth of the fungus was measured individually onall test petri dishes. The results are expressed as % activity relativeto the radial growth on agar without fungicide.

4. Analysis

For each fungicide, a graph was drawn of percentage activity againstconcentration of fungicide in the growth medium. From this graph, theconcentrations of fungicide required to achieve 80% activity wasestimated. These figures are given in the results table.

TABLE 2 Results 1. Coniophora puteana Results. Concentration requiredfor Fungicide 80% Activity in mg/l Azoxystrobin 0.38 Propiconazole 1.8Thiabendazole >5000

Example 3

Mixtures of the strobilurin fungicide azoxystrobin with otherfungicides.

The following compounds and formulations were used:

Active Ingredient (ai) Abbreviation Formulation Fludioxonil FDL SC230Propiconazole PPZ EC250 Azoxystrobin AZO WG50 Thiabendazole TBZ SC500Difenoconazole DFZ EC250

Compounds were tested at different rates, namely for test number006-2005: (100, 50, 12.5, 3.1, 1.6, 0.8, 0.2, 0.05, 0 mg ai/l), and fortest number 015-2005: 200, 100, 25, 12.5, 6.25, 3.12, 1.6, 0.8, 0.4, 0.2mg/l

Test organisms and media used:

Cultivation of Organism fungi Test medium Test conditions All 24° C., onspore suspension in Incubation at 24° C. organisms PDA medium 0.3% AEmedia for 3-6 days

Propagation of the Different Fungi:

Alternaria tenuissima (DSM 63360), Penicillium chrysogenum (DSM 895),Stachybotrys chartarum (DSM2144), Aspergillus niger (DSM 63263),Aspergillus versicolor (DSM 1943) and Aureobasidium pullulans (ATCC15233) were separately cultivated on PDA media to suppress sporulation.Spore suspensions were produced for each fungi. Spore concentrations ofapprox. 100.000 spores/ml were used.

Test method used: liquid culture assay on 24 well plates.

For solo (i.e. single) ai testing the formulated fungicide (100 ul) wasfilled into the 24 well plates and 100 ul distilled water was added.Afterwards 800 ul of 0.3% AE media was added to the plate. The sporesuspension of the specific fungi was added to this media in advancecontaining approx. 100,000 spores/ml. The 24 well plates were sealed andincubated at 24° C.

Dependent on the growth properties of each organisms, the evaluation wasdone after 3 to 6 days, when the surface of the check well was coveredwith mycelium. The evaluation was performed by assessing the growth ofthe fungi related to the check growth. The results are expressed as %activity relative to the check (values of 0-100% growth). Afterwards theresults were converted in % O growth inhibition.

For synergism testing of the 2-way mixtures 100 ul of each fungicidewere filled into 24 well plates and 800 ul of 0.3% AE media containingthe spore suspension was added. Different ratios of the 2 fungiciderates were tested at the same time.

Analysis:

For the mixtures of different fungicides the synergism was calculatedbased on the Colby equation, which is described below:

A synergistic effect exists whenever the action of the active ingredientcombination of the compound of formula I and one or more compounds offormula II is greater than the sum of the actions of the activeingredients applied individually.

The fungicidal action to be expected, We, for a given combination of twofungicides can be calculated as follows (see COLBY, S. R. “Calculatingsynergistic and antagonistic response of herbicide combinations”. Weeds15, pages 20-22; 1967):

We=X+[Y×(100−X)/100]

wherein:X=% activity in the case of treatment with the compound of formula I atrate x, in comparison with untreated control (=0%).Y=% activity in the case of treatment with a compound of formula II atrate y, in comparison with untreated control.We=expected activity (% activity in comparison with untreated control)after treatment with the compound of formula I and a compound of formulaII at a rate of x+y kg of active ingredient.

If the activity actually observed is greater than the expected value We(factor observed activity/expected activity >1.2), there is asynergistic effect. The synergistic effect of the combinations of theactive ingredient of AZO with the active ingredients described above isdemonstrated in the following results.

Results

All rates below are expressed as mg ai/l (i.e. ppm).

Mixtures of azoxystrobin and fludioxonil Fungus inh. % tested Test rate(AZO) rate (FDL) ratio inh % (AZO alone) inh % (FDL alone) (combination)AZO + FDL A. tenuissima 006- 100 0.2 500 30 70 100 2005 AZO + FDL A.tenuissima 006- 0.8 0.2 4 10 70 90 2005 AZO + FDL A. tenuissima 006- 0.20.2 1 10 70 90 2005 AZO + FDL A. tenuissima 006- 0.05 0.2 0.25 10 70 902005 AZO + FDL P. chrysogenum 006- 100 0.05 2000 10 0 30 2005 AZO + FDLP. chrysogenum 006- 50 0.05 1000 10 0 30 2005 AZO + FDL P. chrysogenum006- 12.5 0.05 250 10 0 30 2005 AZO + FDL P. chrysogenum 006- 3.12 0.0562.4 10 0 30 2005 AZO + FDL P. chrysogenum 006- 1.6 0.05 32 10 0 30 2005AZO + FDL P. chrysogenum 006- 0.8 0.05 16 10 0 30 2005 AZO + FDL P.chrysogenum 006- 50 0.2 250 10 50 70 2005 AZO + FDL P. chrysogenum 006-12.5 0.2 62.5 10 50 70 2005 AZO + FDL P. chrysogenum 006- 3.12 0.2 15.610 50 70 2005 AZO + FDL P. chrysogenum 006- 0.8 0.2 4 10 50 70 2005AZO + FDL P. chrysogenum 006- 0.2 0.2 1 0 50 70 2005 AZO + FDL P.chrysogenum 006- 0.05 0.2 0.25 10 50 70 2005 AZO + FDL A. versicolor006- 1.6 0.05 32 30 10 90 2005 AZO + FDL A. versicolor 006- 0.8 0.05 1630 10 90 2005 AZO + FDL A. niger 006- 0.05 0.2 0.25 10 50 70 2005 AZO +FDL A. niger 006- 0.05 0.8 0.0625 10 70 90 2005 AZO + FDL A. niger 006-0.05 1.6 0.031 10 70 90 2005 AZO + FDL A. niger 006- 0.05 3.12 0.016 1070 90 2005 AZO + FDL A. niger 006- 0.05 12.5 0.004 10 70 90 2005 AZO +FDL A. tenuissima 015- 100 100 1 10 70 100 2005 AZO + FDL A. tenuissima015- 50 50 1 10 70 100 2005 AZO + FDL A. tenuissima 015- 25 25 1 10 70100 2005 AZO + FDL A. tenuissima 015- 12.5 12.5 1 10 70 100 2005 AZO +FDL A. tenuissima 015- 6.25 6.25 1 10 50 100 2005 AZO + FDL A.tenuissima 015- 3.1 3.1 1 10 50 100 2005 AZO + FDL A. tenuissima 015-1.6 1.6 1 10 50 100 2005 AZO + FDL A. tenuissima 015- 0.8 0.8 1 10 30100 2005 AZO + FDL A. tenuissima 015- 0.4 0.4 1 10 30 70 2005 AZO + FDLA. tenuissima 015- 100 200 0.5 10 50 100 2005 AZO + FDL A. tenuissima015- 50 100 0.5 10 70 100 2005 AZO + FDL A. tenuissima 015- 25 50 0.5 1070 100 2005 AZO + FDL A. tenuissima 015- 12.5 25 0.5 10 70 100 2005AZO + FDL A. tenuissima 015- 6.25 12.5 0.5 10 70 100 2005 AZO + FDL A.tenuissima 015- 3.1 6.25 0.49 10 50 100 2005 AZO + FDL A. tenuissima015- 1.6 3.1 0.51 10 50 100 2005 AZO + FDL A. tenuissima 015- 0.8 1.60.5 10 50 100 2005 AZO + FDL A. tenuissima 015- 0.4 0.8 0.5 10 30 1002005 AZO + FDL A. tenuissima 015- 200 100 2 10 70 100 2005 AZO + FDL A.tenuissima 015- 100 50 2 10 70 100 2005 AZO + FDL A. tenuissima 015- 5025 2 10 70 100 2005 AZO + FDL A. tenuissima 015- 25 12.5 2 10 70 1002005 AZO + FDL A. tenuissima 015- 12.5 6.25 2 10 50 100 2005 AZO + FDLA. tenuissima 015- 6.25 3.1 2.01 10 50 100 2005 AZO + FDL A. tenuissima015- 3.1 1.6 1.93 10 50 100 2005 AZO + FDL A. tenuissima 015- 1.6 0.8 210 30 100 2005 AZO + FDL A. tenuissima 015- 0.8 0.4 2 10 30 70 2005AZO + FDL A. tenuissima 015- 200 50 4 10 70 100 2005 AZO + FDL A.tenuissima 015- 100 25 4 10 70 100 2005 AZO + FDL A. tenuissima 015- 5012.5 4 10 70 100 2005 AZO + FDL A. tenuissima 015- 25 6.25 4 10 50 1002005 AZO + FDL A. tenuissima 015- 12.5 3.1 4.03 10 50 100 2005 AZO + FDLA. tenuissima 015- 6.25 1.6 3.90 10 50 100 2005 AZO + FDL A. tenuissima015- 3.1 0.8 3.87 10 30 100 2005 AZO + FDL A. tenuissima 015- 1.6 0.4 410 30 100 2005 AZO + FDL A. tenuissima 015- 0.8 0.2 4 10 30 90 2005AZO + FDL A. tenuissima 015- 50 200 0.25 10 50 100 2005 AZO + FDL A.tenuissima 015- 25 100 0.25 10 70 100 2005 AZO + FDL A. tenuissima 015-12.5 50 0.25 10 70 100 2005 AZO + FDL A. tenuissima 015- 6.25 25 0.25 1070 100 2005 AZO + FDL A. tenuissima 015- 3.1 12.5 0.248 10 70 100 2005AZO + FDL A. tenuissima 015- 1.6 6.25 0.256 10 50 100 2005 AZO + FDL A.tenuissima 015- 0.8 3.1 0.258 10 50 100 2005

Mixtures of azoxystrobin and thiabendazole inh % (AZO inh % (TBZ inh. %Fungus tested Test rate (AZO) rate (TBZ) ratio alone) alone)(combination) AZO + TBZ A. tenuissima 015- 200 200 1 30 0 100 2005 AZO +TBZ A. tenuissima 015- 100 100 1 30 0 100 2005 AZO + TBZ A. tenuissima015- 50 50 1 30 0 100 2005 AZO + TBZ A. tenuissima 015- 25 25 1 30 0 502005 AZO + TBZ A. tenuissima 015- 100 200 0.5 30 0 100 2005 AZO + TBZ A.tenuissima 015- 50 100 0.5 30 0 100 2005 AZO + TBZ A. tenuissima 015- 2550 0.5 30 0 100 2005 AZO + TBZ A. tenuissima 015- 200 100 2 30 0 1002005 AZO + TBZ A. tenuissima 015- 100 50 2 30 0 100 2005 AZO + TBZ A.tenuissima 015- 50 25 2 30 0 100 2005 AZO + TBZ A. tenuissima 015- 2512.5 2 30 0 50 2005 AZO + TBZ A. tenuissima 015- 50 200 0.25 30 0 1002005 AZO + TBZ A. tenuissima 015- 25 100 0.25 30 0 100 2005 AZO + TBZ A.tenuissima 015- 12.5 50 0.25 30 0 100 2005 AZO + TBZ A. tenuissima 015-200 50 4 30 0 100 2005 AZO + TBZ A. tenuissima 015- 100 25 4 30 0 1002005 AZO + TBZ A. tenuissima 015- 50 12.5 4 30 0 100 2005

Mixtures of azoxystrobin and propiconazole inh % (AZO inh % (PPZ inh. %Fungus tested Test rate (AZO) rate (PPZ) ratio alone) alone)(combination) AZO + PPZ A. pullulans 006-2005 0.2 3.12 0.064 10 70 90AZO + PPZ A. pullulans 006-2005 0.2 1.6 0.125 10 70 90 AZO + PPZ A.pullulans 006-2005 0.8 12.5 0.064 10 70 90 AZO + PPZ A. pullulans006-2005 0.8 3.12 0.256 10 70 90 AZO + PPZ A. pullulans 006-2005 0.8 1.60.5 10 70 90 AZO + PPZ A. pullulans 006-2005 1.6 12.5 0.128 10 70 90AZO + PPZ A. pullulans 006-2005 1.6 3.12 0.512 10 70 90 AZO + PPZ A.pullulans 006-2005 1.6 1.6 1 10 70 90 AZO + PPZ A. pullulans 006-20053.12 12.5 0.249 10 70 100 AZO + PPZ A. pullulans 006-2005 3.12 3.12 1 1070 90 AZO + PPZ A. pullulans 006-2005 3.12 1.6 1.95 10 70 90 AZO + PPZA. pullulans 006-2005 12.5 12.5 1 10 70 100 AZO + PPZ A. pullulans006-2005 12.5 3.12 4.006 10 70 90 AZO + PPZ S. chartarum 006-2005 0.83.12 0.256 10 10 30 AZO + PPZ S. chartarum 006-2005 0.8 1.6 0.5 10 10 30AZO + PPZ S. chartarum 006-2005 0.8 0.8 1 10 0 30 AZO + PPZ A. pullulans015-2005 50 50 1 0 70 100 AZO + PPZ A. pullulans 015-2005 25 50 0.5 0 70100 AZO + PPZ A. pullulans 015-2005 100 50 2 0 70 100 AZO + PPZ A.pullulans 015-2005 50 25 2 0 50 100 AZO + PPZ A. pullulans 015-2005 12.550 0.25 0 70 100 AZO + PPZ A. pullulans 015-2005 100 25 4 0 50 100

Mixtures of azoxystrobin and difenoconazole inh % (AZO inh % (DFZ inh. %Fungus tested Test rate (AZO) rate (DFZ) ratio alone) alone)(combination) AZO + DFZ A. pullulans 006-2005 0.05 3.12 0.016 0 70 90AZO + DFZ A. pullulans 006-2005 0.2 3.12 0.064 10 70 90 AZO + DFZ A.pullulans 006-2005 0.8 3.12 0.256 10 70 100 AZO + DFZ A. pullulans006-2005 1.6 3.12 0.512 10 70 100 AZO + DFZ A. pullulans 006-2005 3.123.12 1 10 70 100 AZO + DFZ A. pullulans 006-2005 12.5 3.12 4.006 10 70100

Example 4 Mixtures of Azoxystrobin, Thiabendazole and Fludioxonil

The following compounds and formulations were used:

Active Ingredient (ai) Abbreviation Formulation Fludioxonil FDL SC230Azoxystrobin AZO WG50 Thiabendazole TBZ SC500

All compounds were tested at 8 rates, namely for 006-2005: (100, 50,12.5, 3.1, 1.6, 0.8, 0.2, 0.05, 0 mg ai/l), for 015-2005: 200, 100, 25,12.5, 6.25, 3.12, 1.6, 0.8, 0.4, 0.2 mg/l

Test organisms and media used:

Cultivation of Organism fungi Test medium Test conditions all 24° C., onspore suspension in Incubation at 24° C. organisms PDA medium 0.3% AEmedia for 3-6 days

Propagation of the Different Fungi:

For test 006-2005: Alternaria tenuissima (DSM 63360), Penicilliumchrysogenum (DSM 895), Cladosporium cladosporoides (DSM62121),Aspergillus niger (DSM 63263), Aspergillus versicolor (DSM 1943) andAureobasidium pullulans (ATCC 15233) were separately cultivated on PDAmedia to suppress sporulation. Spore suspensions were produced for eachfungus. Spore concentrations of approx. 100,000 spores/ml were used.

For test 015-2006: Alternaria tenuissima (DSM 63360), Penicilliumpinophilum (CBS342.61), Gliocladium virens (DSM1963), Aspergillus niger(DSM 63263), Stachybotrys chartarum (DSM 2144) and Aureobasidiumpullulans (ATCC 15233) were separately cultivated on PDA media tosuppress sporulation. Spore suspensions were produced for each fungus.Spore concentrations of approx. 100,000 spores/ml were used.

Test method used: liquid culture assay on 24 and 48 well platesrespectively.

For testing of the 3 way mixtures each of the formulated fungicide (100ul) was filled into the 24 and 48 well plates respectively. Afterwards700 ul of 0.3% AE media was added to the plate. The spore suspension ofthe specific fungi was added to this media in advance containing approx.100,000 spores/ml. For testing the solo compounds the equivalent ofdistilled water was added instead of the formulated fungicide volume ofthe mixing partners. The plates were then sealed and incubated at 24° C.

Dependent on the growth properties of each organisms, the evaluation wasdone after 3 to 6 days, when the surface of the check well was coveredwith mycelium. The evaluation was performed by assessing the growth ofthe fungi related to the check growth. The results are expressed as %activity relative to the check (values of 0-100% growth). Afterwards theresults were converted in % growth inhibition.

Analysis:

For the mixtures of different fungicides the synergism was calculatedbased on the Colby equation, which is described above.

Results

All rates below are expressed as mg ai/l (i.e. ppm)

Test Number 006-2005 inh % inh % (AZO inh % (FDL (TBZ inh. % Fungustested Test rate (AZO) rate (FDL) rate (TBZ) alone) alone) alone)(combination) AZO + FDL + TBZ A. tenuissima 006- 100 0.2 0.2 10 50 0 702005 AZO + FDL + TBZ A. tenuissima 006- 50 0.2 0.2 10 50 0 70 2005 AZO +FDL + TBZ A. tenuissima 006- 12.5 0.2 0.2 10 50 0 70 2005 AZO + FDL +TBZ A. tenuissima 006- 3.12 0.2 0.2 10 50 0 70 2005 AZO + FDL + TBZ A.tenuissima 006- 1.6 0.2 0.2 10 50 0 70 2005 AZO + FDL + TBZ A.tenuissima 006- 0.8 0.2 0.2 10 50 0 70 2005 AZO + FDL + TBZ A.tenuissima 006- 0.2 0.2 0.2 10 50 0 70 2005 AZO + FDL + TBZ A.tenuissima 006- 0.05 0.2 0.2 10 50 0 70 2005 AZO + FDL + TBZ A.tenuissima 006- 100 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 50 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 12.5 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 3.12 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 1.6 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 0.8 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 0.2 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 0.05 0.8 0.8 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 100 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 50 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 12.5 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 3.12 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 1.6 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 0.8 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 0.2 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.tenuissima 006- 0.05 1.6 1.6 10 70 0 100 2005 AZO + FDL + TBZ A.versicolor 006- 100 0.2 0.2 30 0 0 70 2005 AZO + FDL + TBZ A. versicolor006- 50 0.2 0.2 30 0 0 70 2005 AZO + FDL + TBZ A. versicolor 006- 12.50.2 0.2 30 0 0 70 2005 AZO + FDL + TBZ A. versicolor 006- 3.12 0.2 0.230 0 0 70 2005 AZO + FDL + TBZ A. versicolor 006- 1.6 0.2 0.2 30 0 0 702005 AZO + FDL + TBZ A. versicolor 006- 0.8 0.2 0.2 30 0 0 70 2005 AZO +FDL + TBZ A. versicolor 006- 0.2 0.2 0.2 30 0 0 50 2005 AZO + FDL + TBZA. versicolor 006- 0.05 0.2 0.2 10 0 0 30 2005 AZO + FDL + TBZ A.versicolor 006- 100 0.8 0.8 30 0 0 70 2005 AZO + FDL + TBZ A. versicolor006- 50 0.8 0.8 30 0 0 70 2005 AZO + FDL + TBZ A. versicolor 006- 12.50.8 0.8 30 0 0 70 2005 AZO + FDL + TBZ A. versicolor 006- 3.12 0.8 0.830 0 0 70 2005 AZO + FDL + TBZ A. versicolor 006- 1.6 0.8 0.8 30 0 0 702005 AZO + FDL + TBZ A. versicolor 006- 0.8 0.8 0.8 30 0 0 70 2005 AZO +FDL + TBZ A. versicolor 006- 0.2 0.8 0.8 30 0 0 30 2005 AZO + FDL + TBZA. versicolor 006- 0.05 0.8 0.8 10 0 0 30 2005 AZO + FDL + TBZ A.versicolor 006- 100 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 50 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 12.5 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 3.12 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 1.6 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 0.8 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 0.2 1.6 1.6 30 0 10 100 2005 AZO + FDL + TBZ A.versicolor 006- 0.05 1.6 1.6 10 0 10 100 2005 AZO + FDL + TBZ A. niger006- 0.05 0.8 0.8 10 50 0 90 2005

Test Number 015-2005 inh % inh % (AZO inh % (FDL (TBZ inh. % Fungustested Test rate (AZO) rate (FDL) rate (TBZ) alone) alone) alone)(combination) AZO + FDL + TBZ A. niger 015- 0.05 0.8 0.8 0 50 0 70 2005AZO + FDL + TBZ A. niger 015- 0.05 0.8 0.2 0 50 0 70 2005 AZO + FDL +TBZ A. niger 015- 0.05 1.6 0.8 0 50 0 70 2005 AZO + FDL + TBZ A. niger015- 0.05 1.6 0.2 0 50 0 70 2005 AZO + FDL + TBZ A. niger 015- 0.05 3.10.8 0 50 0 70 2005 AZO + FDL + TBZ A. niger 015- 0.05 3.1 0.2 0 50 0 702005 AZO + FDL + TBZ A. tenuissima 015- 0.05 0.8 100 10 50 0 100 2005AZO + FDL + TBZ A. tenuissima 015- 0.05 0.8 25 10 50 0 100 2005 AZO +FDL + TBZ A. tenuissima 015- 0.05 0.8 6.25 10 50 0 100 2005 AZO + FDL +TBZ A. tenuissima 015- 0.05 0.8 3.1 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 0.8 1.6 10 50 0 90 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 0.8 0.2 10 50 0 90 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 1.6 100 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 1.6 25 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 1.6 6.25 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 1.6 3.1 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 1.6 1.6 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.05 1.6 0.2 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.2 0.8 100 10 50 0 90 2005 AZO + FDL + TBZ A.tenuissima 015- 0.2 0.8 25 10 50 0 90 2005 AZO + FDL + TBZ A. tenuissima015- 0.2 0.8 6.25 10 50 0 100 2005 AZO + FDL + TBZ A. tenuissima 015-0.2 0.8 3.1 10 50 0 100 2005 AZO + FDL + TBZ A. tenuissima 015- 0.2 0.81.6 10 50 0 100 2005 AZO + FDL + TBZ A. tenuissima 015- 0.2 0.8 0.2 1050 0 100 2005 AZO + FDL + TBZ A. tenuissima 015- 0.2 1.6 100 10 50 0 1002005 AZO + FDL + TBZ A. tenuissima 015- 0.2 1.6 25 10 50 0 100 2005AZO + FDL + TBZ A. tenuissima 015- 0.2 1.6 6.25 10 50 0 100 2005 AZO +FDL + TBZ A. tenuissima 015- 0.2 1.6 3.1 10 50 0 100 2005 AZO + FDL +TBZ A. tenuissima 015- 0.2 1.6 1.6 10 50 0 100 2005 AZO + FDL + TBZ A.tenuissima 015- 0.2 1.6 0.2 10 50 0 100 2005 AZO + FDL + TBZ S.chartarum 015- 0.8 0.05 25 10 10 30 100 2005 AZO + FDL + TBZ S.chartarum 015- 0.8 0.05 6.25 10 10 10 100 2005 AZO + FDL + TBZ S.chartarum 015- 0.8 0.05 3.1 10 10 0 100 2005 AZO + FDL + TBZ S.chartarum 015- 1.6 0.05 6.25 10 10 10 100 2005 AZO + FDL + TBZ S.chartarum 015- 1.6 0.05 3.1 10 10 10 100 2005 AZO + FDL + TBZ S.chartarum 015- 3.1 0.2 25 30 50 30 100 2005 AZO + FDL + TBZ S. chartarum015- 3.1 0.2 6.25 30 50 10 100 2005 AZO + FDL + TBZ S. chartarum 015-3.1 0.2 3.1 30 50 0 100

Example 5 Hand Sheets Efficacy Testing

Preparation of the Hand Sheets:

The hand sheets are made using 80% OCC pulp concentrate (old corrugatedcartons)+20% ONP (old newspapers) pulp concentrate plus additionalingredients. The fungicides are added during preparation by mixing andthen the hand sheets are dried.

The following compounds and formulations may be used:

Active Ingredient (ai) Abbreviation Formulation Fludioxonil FDL 4FSAzoxystrobin AZO SC250 Thiabendazole TBZ MP340

For efficacy testing the test organisms are cultivated separately on PDAmedia to suppress sporulation. Spore suspensions are produced for eachfingi (spore concentrations of approximately 10⁶/ml). Organisms whichmay be used include Chaetomium globosum (ATCC 6205), Penicilliumcitrinum (ATCC 9849), Stachybotrys chartarum (ATCC16026) and Aspergillusniger (DSM 6275) as pure culture but also as mixed inoculum.

Mineral agar (according to ASTM G21-96) can be used as test media.Before inoculation the hand sheets are divided in 5 pieces each, eachpiece is placed in a separate dish and then inoculated with the fungi.The samples are then incubated at 30° C. for 28 days. Pre-reading of thesamples may be performed at approximately 10 days after inoculation. Theactivity of the treatments may be assessed visually, using a ratingsystem of 0-100% growth inhibition of fungal growth. For the mixtures ofdifferent fungicides the synergism can be calculated based on the Colbyequation, which is described above.

1.-50. (canceled)
 51. A composition comprising as active ingredients, synergistic amounts of the fungicides (a) azoxystrobin and (b) thiabendazole.
 52. A composition according to claim 51, further comprising fludioxonil.
 53. The composition according to claim 51 suitable for use in the treatment of wallboard.
 54. A paper product comprising a composition according to claim
 51. 55. A wallboard that has been treated with a fungicidally effective amount of a composition according to claim
 51. 56. Wallboard according to claim 55 wherein the fungicides are included in the gypsum core.
 57. Wallboard according to claim 55 wherein the fungicides are included in the paper coating of the wallboard.
 58. Wallboard according to claim 55 wherein the fungicides are applied after the wallboard is made.
 59. A building material treated with a fungicidally effective amount of a composition according to claim
 51. 60. A building material according to claim 59 wherein said building material means structural timber, engineered wood, plastic, polyvinyl chloride, polyurethane, paint and wood plastic composite.
 61. A method for the prevention and/or treatment of growth and/or infestation of a fungus on a wallboard comprising treating said wallboard with a fungicidally effective amount of a composition according to claim
 51. 62. A method according to claim 61 wherein the fungicides are included in the paper during the papermaking process.
 63. A method for the prevention of fungal infection induced wet-rot in wood comprising treating said wood with a composition according to claim
 51. 64. A method for the prevention and/or treatment of Coniophora puteana growth/infestation on wood comprising treating said wood with a fungicidally effective amount of a composition according to claim
 51. 